摘要/Abstract
以过氧化叔丁醇为氧化剂，以钴（II）与含N配体为催化体系催化氧化2-乙基-3-甲基吡嗪（EMP），提出一种具有放大应用前景的2-乙酰基-3-甲基吡嗪绿色制备方法.考察了过渡金属催化剂的种类、配体种类、溶剂、温度等反应条件对催化氧化过程的影响，在最优反应条件下EMP转化率可达58.8%，2-乙酰基-3-甲基吡嗪（AMP）选择性92.2%.研究了该反应体系催化氧化EMP的反应机理，建立了该反应的拟均相反应动力学模型.在以上实验基础上，对该反应体系进行了放大实验研究，结果表明该新方法具有较好的工业放大前景，但反应温度的控制是放大过程的关键因素.
关键词: 2-乙基-3-甲基吡嗪(EMP), 2-乙酰基-3-甲基吡嗪(AMP), 烯丙基氧化, 反应机理, 动力学, 工艺放大
A green and scalable oxidation of 2-ethyl-3-methylpyrazine (EMP) by tert-butylhydroperoxide was investigated with a catalytic system of cobalt(II) and N-containing ligand. The effects of catalyst, ligand, solvent and temperature were compared, and the catalysis system of cobalt(II) acetylacetonate and 2,2-bipyridine gave the highest selectivity. Mechanistic study of this catalysis system suggested that the oxidation of EMP followed a free radical oxidation pathway, and a homogeneous reaction kinetics model was established to calculate the reaction rate constant and activation energy. The scale-up of the oxidation system was performed to check the scalability of the oxidation reaction, and the temperature control of the system was the key part of the process.
Key words: 2-ethyl-3-methylpyrazine (EMP), 2-acetyl-3-methylpyrazine (AMP), allylic oxidation, reaction mechanism, kinetics, scale-up
PDF全文下载地址:
点我下载PDF
